Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids

Definitions

• perfluorinated vinyl ethers with an ester group at the other end of the molecule are important monomers, the copolymers of which with tetrafluoroethylene and other fluoroolefins are used to produce ion-selective membranes, cation exchange compositions and fluoroelastomers.
• w-fluorosulfato-perfluoro are therefore according to the above carboxylic acid derivatives (especially the esters) or perfluorinated dicarboxylic acid fluoride esters are important key substances.
• the task was therefore to open up an improved route to the perfluorinated vinyl ethers with yet another functional group - in particular an ester group - in the molecule.
• the process mainly provides the 2: 1 adducts from the corresponding perfluorinated ⁇ -olefins and peroxodisulfuryl difluoride.
• 1,4-bis-fluorosulfato-perfluorobutane is therefore the main product:
• catalysts are the alkali metal fluorides and / or alkali metal hydrogen fluorides, the Na and K compounds being preferred.
• a catalytic amount of the alkali metal fluoride and / or alkali metal hydrogen fluoride - generally between about 0.1 and 30 mol%, based on the starting bisfluorosulfato-perfluoroalkane VIII, is sufficient.
• temperatures between approximately -30 and + 150 ° C. are suitable as reaction temperatures, temperatures between approximately 20 and 120 ° C. being preferred.
• a catalytic to about equimolar amount of alkali metal fluoride and / or alkali metal hydrogen fluoride - generally between about 0.1 and 100 mol%, preferably between about 1 and 30 mol%, based on the starting bisfluorosulfato-perfluoroalkane VIII - be used.
• an inert diluent which does not dissolve the alkali metal fluorides and / or hydrogen fluoride, in addition to an at least approximately equimolar amount of the alcohol of the formula IX which is required as a reactant.
• diluents e.g. halogenated hydrocarbons such as methylene chloride etc. can be used.
• An expedient way of carrying out variant b) is, for example, to combine the starting bisfluorosulfato-perfluoroalkane VIII, the alcohol IX and the alkali fluoride and / or hydrogen fluoride and, if appropriate, the diluent at low temperature and to slowly warm them up or let them warm up. After the calculated amount of sulfuryl fluoride SO 2 F 2 has arisen (measurement approx a gas clock!), the alkali fluoride and / or hydrogen fluoride is filtered off, washed with water free of alcohol and acid, dried and distilled.
• hydrofluoric acid also forms as a reaction product, in particular in process variant b), it is particularly advisable here to work in vessels made of a material which is resistant to hydrofluoric acid.
• Example 2 In an apparatus as described in Example 1, 398 g (1.0 mol) of 1,4-bisfluorosulfato-perfluorobutane, 1.16 g (0.02 mol) of dry potassium fluoride and 0.84 g (0.02 mol) of sodium fluoride are added. The mixture is then heated to 100-120 ° C. After a short time, gas evolution begins and reflux occurs in the column. The transition liquid has a boiling point of 75 - 80 ° C. Working up is carried out as in Example 1. 196 g (66%) of 4-fluorosulfato-perfluorobutanoic acid fluoride are obtained.
• Methyl 4-fluorosulfato-perfluorobutanoate FSO 2 -O-CF 2 -CF 2 -CF 2 -COOCH 3 with further conversion to 3-carbomethoxy-perfluoropropanoic acid fluoride FOC-CF 2 -CF 2 -COOCH 3
• Methyl 4-fluorosulfato-perfluorobutanoate FSO 2 -O-CF 2 -CF 2 -CF 2 -COOCH 3 with further conversion to 3-carbomethoxyperfluoropropanoic acid fluoride FOC-CF 2 -CF 2 -COOCH 3
• Example 5 100 g (0.25 mol) of 1,4-bisfluorosulfato-perfluorobutane are added with 3.9 g (0.05 mol) of potassium hydrogen fluoride in a mixture of 100 ml of methanol and 100 ml of methylene chloride at initially 0-10 ° C. later at around 20 ° C. After the evolution of gas has ended, the salt is filtered off and worked up as described in Example A5. 62 g of distillate with bp 139-176 ° C./755 mm are obtained, which, after reaction with 0.58 g (0.01 mol) of potassium fluoride, gives 24 g (46%) of 3-carbomethoxyperfluoropropanoic acid fluoride.
• Example B4 According to the procedure in Example B4, 130 g (0.32 mol) of methyl 6-fluorosulfato-perfluorohexanoate are reacted with 0.58 g (0.01 mol) of dry potassium fluoride. The sulfuryl fluoride is split off between 80 and 120 ° C. The distillation gives 94 g (96%) of 5-carbomethoxyperfluoropentanoic acid fluoride with bp 62-63 ° C / 48 mm.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

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• 1981
  • 1981-07-16 DE DE19813128119 patent/DE3128119A1/de not_active Withdrawn
• 1982
  • 1982-07-10 DE DE8282106201T patent/DE3275719D1/de not_active Expired
  • 1982-07-10 EP EP82106201A patent/EP0070485B1/fr not_active Expired
  • 1982-07-14 US US06/398,118 patent/US4454072A/en not_active Expired - Fee Related
  • 1982-07-15 JP JP57122259A patent/JPS5818355A/ja active Granted
  • 1982-07-15 CA CA000407312A patent/CA1206161A/fr not_active Expired

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